U.S. patent application number 15/514160 was filed with the patent office on 2017-10-26 for cyclic olefin ring-opened polymer hydride, resin molded article, and optical member.
This patent application is currently assigned to Zeon Corporation. The applicant listed for this patent is ZEON CORPORATION. Invention is credited to Akira FURUKO, Takashi HOUKAWA, Ayumi SATO, Kenji UMEDA.
Application Number | 20170306080 15/514160 |
Document ID | / |
Family ID | 55630340 |
Filed Date | 2017-10-26 |
United States Patent
Application |
20170306080 |
Kind Code |
A1 |
FURUKO; Akira ; et
al. |
October 26, 2017 |
CYCLIC OLEFIN RING-OPENED POLYMER HYDRIDE, RESIN MOLDED ARTICLE,
AND OPTICAL MEMBER
Abstract
The present invention is a hydrogenated cycloolefin ring-opening
polymer comprising a repeating unit derived from
tetracyclododecene, and a repeating unit derived from an additional
norbornene-based monomer, the hydrogenated cycloolefin ring-opening
polymer having a racemo diad ratio of 65% or more with respect to
the repeating unit derived from tetracyclododecene, the
hydrogenated cycloolefin ring-opening polymer having a weight
average molecular weight (Mw) of 10,000 to 40,000, and a resin
formed article obtained by forming the hydrogenated cycloolefin
ring-opening polymer having a glass transition temperature of 140
to 165.degree. C., a melt flow rate of 8 g/10 min or more as
measured at a temperature of 280.degree. C. under a load of 21.18
N, and a flexural strength of 60 MPa or more as measured by a
flexural test at a test speed of 2 mm/min, and a resin formed
article, and an optical member.
Inventors: |
FURUKO; Akira; (Chiyoda-ku,
Tokyo, JP) ; HOUKAWA; Takashi; (Chiyoda-ku, Tokyo,
JP) ; SATO; Ayumi; (Chiyoda-ku, Tokyo, JP) ;
UMEDA; Kenji; (Chiyoda-ku, Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ZEON CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
Zeon Corporation
Tokyo
JP
|
Family ID: |
55630340 |
Appl. No.: |
15/514160 |
Filed: |
September 24, 2015 |
PCT Filed: |
September 24, 2015 |
PCT NO: |
PCT/JP2015/076944 |
371 Date: |
March 24, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 61/08 20130101;
G02B 1/041 20130101; C08G 2261/228 20130101; C08G 2261/3325
20130101; C08G 2261/3324 20130101; C08G 2261/418 20130101; C08G
2261/724 20130101; C08G 2261/592 20130101; C08G 2261/124
20130101 |
International
Class: |
C08G 61/08 20060101
C08G061/08; G02B 1/04 20060101 G02B001/04 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 29, 2014 |
JP |
2014-198133 |
Claims
1. A hydrogenated cycloolefin ring-opening polymer comprising a
repeating unit derived from tetracyclododecene, and a repeating
unit derived from an additional norbornene-based monomer, the
hydrogenated cycloolefin ring-opening polymer comprising the
repeating unit derived from tetracyclododecene in a ratio of 55 wt
% or more and less than 100 wt % based on the total amount of
repeating units, and comprising the repeating unit derived from the
additional norbornene-based monomer in a ratio of more than 0 wt %
and 45 wt % or less based on the total amount of repeating units,
the hydrogenated cycloolefin ring-opening polymer having a racemo
diad ratio of 65% or more with respect to the repeating unit
derived from tetracyclododecene, the hydrogenated cycloolefin
ring-opening polymer having a weight average molecular weight (Mw)
of 10,000 to 40,000, and a resin formed article obtained by forming
the hydrogenated cycloolefin ring-opening polymer having a glass
transition temperature of 140 to 165.degree. C., a melt flow rate
of 8 g/10 min or more as measured in accordance with JIS K 6719 at
a temperature of 280.degree. C. under a load of 21.18 N, and a
flexural strength of 60 MPa or more as measured by a flexural test
in accordance with JIS K 7171 at a test speed of 2 mm/min.
2. The hydrogenated cycloolefin ring-opening polymer according to
claim 1, the hydrogenated cycloolefin ring-opening polymer
comprising a repeating unit derived from a polycyclic
norbornene-based monomer that has a polycyclic structure having
three or more rings in a ratio of 95 wt % or more based on the
total amount of repeating units.
3. A resin formed article obtained by forming a resin composition
that comprises the hydrogenated cycloolefin ring-opening polymer
according to claim 1.
4. The resin formed article according to claim 3, the resin formed
article having a glass transition temperature of 140 to 165.degree.
C., a melt flow rate of 8 g/10 min or more as measured in
accordance with JIS K 6719 at a temperature of 280.degree. C. under
a load of 21.18 N, and a flexural strength of 60 MPa or more as
measured by a flexural test in accordance with JIS K 7171 at a test
speed of 2 mm/min.
5. An optical member comprising the resin formed article according
to claim 3.
Description
TECHNICAL FIELD
[0001] The present invention relates to a hydrogenated cycloolefin
ring-opening polymer that exhibits excellent thermal yellowing
resistance (i.e., the hydrogenated cycloolefin ring-opening polymer
rarely yellows even when allowed to stand at a high temperature for
a long time), excellent high-temperature dimensional stability
(i.e., the hydrogenated cycloolefin ring-opening polymer rarely
changes in size even when allowed to stand at a high temperature
for a long time), and excellent formability, a formed article
(resin formed article) obtained using the hydrogenated cycloolefin
ring-opening polymer, and an optical member that includes the resin
formed article.
BACKGROUND ART
[0002] In recent years, a camera and the like have been installed
in automobiles and the like in order to determine the environment,
and record travel information and the like.
[0003] Since the temperature inside automobiles and the like
increases to a large extent depending on the season, a raw material
for producing a lens used for such a camera is required to exhibit
excellent thermal yellowing resistance and excellent
high-temperature dimensional stability in addition to excellent
optical characteristics (e.g., transparency).
[0004] A hydrogenated cycloolefin ring-opening polymer is known as
a resin that exhibits excellent transparency and excellent
high-temperature dimensional stability.
[0005] For example, Patent Literature 1 discloses a hydrogenated
tetracyclododecene ring-opening polymer that includes a repeating
unit (A) derived from tetracyclododecene in a ratio of 55 to 100
mol % based on the total amount of repeating units, includes a
repeating unit (B) derived from an additional norbornene compound
in a ratio of 0 to 45 mol % based on the total amount of repeating
units, and exhibits excellent solubility in an organic solvent.
[0006] The hydrogenated tetracyclododecene ring-opening polymer
disclosed in Patent Literature 1 has a high glass transition
temperature, and exhibits excellent high-temperature dimensional
stability.
CITATION LIST
Patent Literature
[0007] Patent Literature 1: JP-A-2007-137935
SUMMARY OF INVENTION
Technical Problem
[0008] A hydrogenated tetracyclododecene ring-opening polymer
normally has a high glass transition temperature, and exhibits
excellent high-temperature dimensional stability.
[0009] However, a hydrogenated tetracyclododecene ring-opening
polymer tends to exhibit inferior formability. Specifically, when a
resin formed article is produced using a hydrogenated
tetracyclododecene ring-opening polymer, a significant weld line
(i.e., a thin line that occurs in a molten resin merge-fusion area
within a mold (die) when forming a resin) may be observed. When a
hydrogenated polymer is produced by copolymerizing
tetracyclododecene and an additional cycloolefin monomer, or
produced to have a reduced molecular weight in order to improve
formability and the like, the resulting hydrogenated polymer may
exhibit inferior thermal yellowing resistance or strength, or may
exhibit inferior high-temperature dimensional stability.
[0010] The invention was conceived in view of the above situation.
An object of the invention is to provide a hydrogenated cycloolefin
ring-opening polymer that exhibits excellent thermal yellowing
resistance, excellent high-temperature dimensional stability, and
excellent formability, a resin formed article obtained using the
hydrogenated cycloolefin ring-opening polymer, and an optical
member that includes the resin formed article.
Solution to Problem
[0011] The inventors conducted extensive studies with regard to a
hydrogenated cycloolefin ring-opening polymer that includes a
repeating unit derived from tetracyclododecene in order to solve
the above problem. As a result, the inventors found that a
hydrogenated cycloolefin ring-opening polymer that includes a
repeating unit derived from tetracyclododecene, and a repeating
unit derived from an additional norbornene-based monomer, the
hydrogenated cycloolefin ring-opening polymer including the
repeating unit derived from tetracyclododecene in a ratio of 55 wt
% or more and less than 100 wt % based on the total amount of
repeating units, including the repeating unit derived from the
additional norbornene-based monomer in a ratio of more than 0 wt %
and 45 wt % or less based on the total amount of repeating units,
having a racemo diad ratio of 65% or more with respect to the
repeating unit derived from tetracyclododecene, and having a weight
average molecular weight (Mw) of 10,000 to 40,000, and a resin
formed article obtained by forming the hydrogenated cycloolefin
ring-opening polymer having a glass transition temperature, a melt
flow rate, and a flexural strength within specific ranges, exhibits
excellent thermal yellowing resistance, excellent high-temperature
dimensional stability, and excellent formability. This finding has
led to the completion of the invention.
[0012] Several aspects of the invention provide the following
hydrogenated cycloolefin ring-opening polymer (see (1) and (2)),
resin formed article (see (3)), and optical member (see (4)).
(1) A hydrogenated cycloolefin ring-opening polymer including a
repeating unit derived from tetracyclododecene, and a repeating
unit derived from an additional norbornene-based monomer,
[0013] the hydrogenated cycloolefin ring-opening polymer including
the repeating unit derived from tetracyclododecene in a ratio of 55
wt % or more and less than 100 wt % based on the total amount of
repeating units, and including the repeating unit derived from the
additional norbornene-based monomer in a ratio of more than 0 wt %
and 45 wt % or less based on the total amount of repeating
units,
[0014] the hydrogenated cycloolefin ring-opening polymer having a
racemo diad ratio of 65% or more with respect to the repeating unit
derived from tetracyclododecene,
[0015] the hydrogenated cycloolefin ring-opening polymer having a
weight average molecular weight (Mw) of 10,000 to 40,000, and
[0016] a resin formed article obtained by forming the hydrogenated
cycloolefin ring-opening polymer having a glass transition
temperature of 140 to 165.degree. C., a melt flow rate of 8 g/10
min or more as measured in accordance with JIS K 6719 at a
temperature of 280.degree. C. under a load of 21.18 N, and a
flexural strength of 60 MPa or more as measured by a flexural test
in accordance with JIS K 7171 at a test speed of 2 mm/min.
(2) The hydrogenated cycloolefin ring-opening polymer according to
(1), the hydrogenated cycloolefin ring-opening polymer including a
repeating unit derived from a polycyclic norbornene-based monomer
that has a polycyclic structure having three or more rings in a
ratio of 95 wt % or more based on the total amount of repeating
units. (3) A resin formed article obtained by forming a resin
composition that includes the hydrogenated cycloolefin ring-opening
polymer according to (1) or (2). (4) The resin formed article
according to (3), the resin formed article having a glass
transition temperature of 140 to 165.degree. C., a melt flow rate
of 8 g/10 min or more as measured in accordance with JIS K 6719 at
a temperature of 280.degree. C. under a load of 21.18 N, and a
flexural strength of 60 MPa or more as measured by a flexural test
in accordance with JIS K 7171 at a test speed of 2 mm/min. (5) An
optical member including the resin formed article according to (3)
or (4).
Advantageous Effects of Invention
[0017] The aspects of the invention thus provide a hydrogenated
cycloolefin ring-opening polymer that exhibits excellent thermal
yellowing resistance, excellent high-temperature dimensional
stability, and excellent formability, a resin formed article
obtained using the hydrogenated cycloolefin ring-opening polymer,
and an optical member that includes the resin formed article.
BRIEF DESCRIPTION OF DRAWINGS
[0018] FIG. 1 is a view illustrating the lens mold used in
connection with the examples.
DESCRIPTION OF EMBODIMENTS
[0019] A hydrogenated cycloolefin ring-opening polymer, a resin
formed article, and an optical member according to the exemplary
embodiments of the invention are described in detail below.
1) Hydrogenated Cycloolefin Ring-Opening Polymer
[0020] A hydrogenated cycloolefin ring-opening polymer according to
one embodiment of the invention includes a repeating unit derived
from tetracyclododecene, and a repeating unit derived from an
additional norbornene-based monomer,
[0021] the hydrogenated cycloolefin ring-opening polymer including
the repeating unit derived from tetracyclododecene in a ratio of 55
wt % or more and less than 100 wt % based on the total amount of
repeating units, and including the repeating unit derived from the
additional norbornene-based monomer in a ratio of more than 0 wt %
and 45 wt % or less based on the total amount of repeating
units,
[0022] the hydrogenated cycloolefin ring-opening polymer having a
racemo diad ratio of 65% or more with respect to the repeating unit
derived from tetracyclododecene,
[0023] the hydrogenated cycloolefin ring-opening polymer having a
weight average molecular weight (Mw) of 10,000 to 40,000, and
[0024] a resin formed article obtained by forming the hydrogenated
cycloolefin ring-opening polymer having a glass transition
temperature of 140 to 165.degree. C., a melt flow rate of 8 g/10
min or more as measured in accordance with JIS K 6719 at a
temperature of 280.degree. C. under a load of 21.18 N, and a
flexural strength of 60 MPa or more as measured by a flexural test
in accordance with JIS K 7171 at a test speed of 2 mm/min.
Structure of Hydrogenated Cycloolefin Ring-Opening Polymer
[0025] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention includes the repeating unit
derived from tetracyclododecene (hereinafter may be referred to as
"repeating unit (A)"), and the repeating unit derived from the
additional norbornene-based monomer (hereinafter may be referred to
as "repeating unit (B)").
[0026] The repeating unit (A) included in the hydrogenated
cycloolefin ring-opening polymer according to one embodiment of the
invention is represented by the following formula (1).
##STR00001##
[0027] The repeating unit (A) is formed as described below.
Specifically, tetracyclododecene represented by the following
formula (2) is subjected to ring-opening polymerization.
##STR00002##
[0028] The carbon-carbon double bonds included in the main chain of
the resulting ring-opening polymer are hydrogenated to form the
repeating unit (A).
[0029] The hydrogenated cycloolefin ring-opening polymer includes
the repeating unit (A) in a ratio of 55 wt % or more and less than
100 wt %, preferably 55 to 90 wt %, and more preferably 60 to 85 wt
%, based on the total amount of repeating units.
[0030] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention that includes the repeating unit
(A) in a ratio of 55 wt % or more, exhibits excellent thermal
yellowing resistance and high-temperature dimensional
stability.
[0031] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention has a racemo diad ratio of 65%
or more, preferably 70% or more, and more preferably 75% or more,
with respect to the repeating unit (A).
[0032] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention that has such a controlled
steric structure, exhibits excellent solubility in an organic
solvent, and can be produced with high productivity on an
industrial scale.
[0033] The racemo diad ratio in the hydrogenated cycloolefin
ring-opening polymer may be determined by subjecting the
hydrogenated cycloolefin ring-opening polymer to .sup.13C-NMR
measurement at 100.degree. C. using deuterated o-dichlorobenzene as
a solvent, and calculating the racemo diad ratio based on the
intensity ratio of the signal (51.82 ppm) attributed to racemo
diads to the signal (51.77 ppm) attributed to meso diads.
[0034] Note that the position of each signal may differ to some
extent from the above position depending on the type of repeating
unit (B) and the measurement conditions, but the racemo diad ratio
can be basically calculated as described above.
[0035] The hydrogenated cycloolefin ring-opening polymer that has a
racemo diad ratio of 65% or more with respect to the repeating unit
(A) can be efficiently produced by utilizing a polymerization
catalyst that includes the transition metal imide compound
described later when effecting the ring-opening polymerization
reaction.
[0036] The repeating unit (B) included in the hydrogenated
cycloolefin ring-opening polymer according to one embodiment of the
invention is a repeating unit derived from a norbornene-based
monomer other than tetracyclododecene. The term "norbornene-based
monomer" used herein refers to a monomer that includes the
norbornene skeleton represented by the following formula (3).
##STR00003##
[0037] Examples of the repeating unit (B) include a repeating unit
represented by the following formula (4), and
##STR00004##
a repeating unit represented by the following formula (5).
##STR00005##
[0038] Each of R.sup.1 to R.sup.4 in the formula (4) independently
represents a hydrogen atom, a hydrocarbon group having 1 to 20
carbon atoms, or a substituent that includes a halogen atom, a
silicon atom, an oxygen atom, or a nitrogen atom, and R.sup.2 and
R.sup.3 are optionally bonded to each other to form a ring. R.sup.1
and R.sup.2 or R.sup.3 and R.sup.4 are optionally bonded to each
other to form an alkylidene group. m represents an integer from 0
to 2.
[0039] Note that a case where m is 1 and all of R.sup.1 to R.sup.4
are hydrogen atoms (i.e., a case where the repeating unit
represented by the formula (4) is a repeating unit derived from
tetracyclododecene) is excluded.
[0040] Examples of the hydrocarbon group having 1 to 20 carbon
atoms that may be represented by R.sup.1 to R.sup.4 include an
alkyl group such as a methyl group, an ethyl group, an n-propyl
group, an n-butyl group, a t-butyl group, an n-pentyl group, an
n-hexyl group, and an n-decyl group; a cycloalkyl group such as a
cyclopentyl group and a cyclohexyl group; an alkylidene group such
as a methylidyne group and an ethylidene group; an alkenyl group
such as a vinyl group and a propenyl group; a cycloalkenyl group
such as a cyclohexenyl group and a cyclopentenyl group; an alkynyl
group such as an ethynyl group and a propargyl group; an aryl group
such as a phenyl group; and the like.
[0041] Examples of the substituent that includes a halogen atom, a
silicon atom, an oxygen atom, or a nitrogen atom, include an alkoxy
group such as a methoxy group and an ethoxy group; a hydroxy group;
a hydroxyalkyl group such as a hydroxymethyl group and a
2-hydroxyethyl group; a carboxy group; an alkoxycarbonyl group such
as a methoxycarbonyl group and an ethoxycarbonyl group; a cyano
group; a trialkylsilyl group such as a trimethylsilyl group; a
trialkoxysilyl group such as a trimethoxysilyl group; a halogen
atom such as a fluorine atom, a chlorine atom, a bromine atom, and
an iodine atom; and the like.
[0042] The repeating unit (B) is formed by subjecting one type or
two or more types of corresponding norbornene-based monomer to
ring-opening polymerization, and hydrogenating the carbon-carbon
double bonds included in the main chain and the side chain of the
resulting ring-opening polymer, for example.
[0043] Examples of the norbornene-based monomer include a bicyclic
norbornene-based monomer such as bicyclo[2.2.1]hept-2-ene (trivial
name: norbornene) and 5-ethylidenebicyclo[2.2.1]hept-2-ene (trivial
name: ethylidenenorbornene); a tricyclic norbornene-based monomer
such as tricyclo[4.3.0.sup.1.60.1.sup.2.5]deca-3,7-diene (trivial
name: dicyclopentadiene); a tetracyclic norbornene-based monomer
such as 6-ethylidene-2-tetracyclododecene and
7,8-benzotricyclo[4.3.0.1.sup.2.5]dec-3-ene (trivial name:
methanotetrahydrofluorene (also referred to as
1,4-methano-1,4,4a,9a-tetrahydrofluorene)); and the like.
[0044] The hydrogenated cycloolefin ring-opening polymer includes
the repeating unit (B) in a ratio of more than 0 wt % and 45 wt %
or less, preferably 10 to 45 wt %, and more preferably 15 to 40 wt
%, based on the total amount of repeating units.
[0045] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention that includes the repeating unit
(B), exhibits strength and formability in a well-balanced manner.
The hydrogenated cycloolefin ring-opening polymer according to one
embodiment of the invention that includes the repeating unit (B) in
a ratio of 45 wt % or less, exhibits excellent thermal yellowing
resistance and high-temperature dimensional stability.
[0046] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention preferably includes a repeating
unit derived from a polycyclic norbornene-based monomer that has a
polycyclic structure having three or more rings (including a
repeating unit derived from tetracyclododecene) in a ratio of 95 wt
% or more, more preferably 98 wt % or more, and still more
preferably 100 wt %, based on the total amount of repeating units.
The polycyclic norbornene-based monomer that has a polycyclic
structure having three or more rings is preferably a monomer
selected from the group consisting of a tricyclic norbornene-based
monomer and a tetracyclic norbornene-based monomer.
[0047] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention preferably includes a repeating
unit derived from a tetracyclic norbornene-based monomer (including
a repeating unit derived from tetracyclododecene) in a ratio of 90
wt % or more, and more preferably 95 wt % or more, based on the
total amount of repeating units.
[0048] A hydrogenated cycloolefin ring-opening polymer that meets
these requirements exhibits thermal yellowing resistance,
high-temperature dimensional stability, and formability in a
further well-balanced manner.
Method for Producing Hydrogenated Cycloolefin Ring-Opening
Polymer
[0049] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention may be produced using an
arbitrary method. For example, the desired hydrogenated cycloolefin
ring-opening polymer can be obtained by subjecting
tetracyclododecene and the additional norbornene-based monomer to a
ring-opening polymerization reaction in the presence of a
polymerization catalyst, and hydrogenating the carbon-carbon double
bonds included in the resulting cycloolefin ring-opening polymer in
the presence of a hydrogenation catalyst.
[0050] The polymerization catalyst is not particularly limited. It
is preferable to use a polymerization catalyst that includes a
transition metal imide compound having a structure in which an
alkyl imide or an aryl imide (i.e., ligand) is bonded to a
transition metal among the transition metals that belong to Group 6
in the periodic table, since it is possible to easily obtain a
hydrogenated tetracyclododecene-based ring-opening polymer that has
a racemo diad ratio of 65% or more with respect to the repeating
unit (A).
[0051] Examples of the transition metal imide compound include a
compound represented by the following formula (6).
R.sup.5--N=M.sup.1(L.sup.1).sub.a(X.sup.1).sub.b (6)
[0052] In the formula (6), M.sup.1 represents a transition metal
(transition metal atom) among the transition metals (transition
metal atoms) that belong to Group 6 in the periodic table, L.sup.1
represents a neutral ligand, and X.sup.1 represents an anionic
ligand. R.sup.5 represents a substituted or unsubstituted alkyl
group having 1 to 20 carbon atoms, or a substituted or
unsubstituted aryl group.
[0053] a is 0, 1, or 2, and b is an integer from 1 to 4.
[0054] When a is 2, L.sup.1 are either identical to or different
from each other, and are optionally bonded to each other to form a
chelate ligand.
[0055] When b is 2 or more, X.sup.1 are either identical to or
different from each other, and are optionally bonded to each other
to form a chelate ligand.
[0056] R.sup.5 is optionally bonded to either or both of L.sup.1
and X.sup.1 to form a chelate ligand.
[0057] The transition metal among the transition metals that belong
to Group 6 in the periodic table that is represented by M.sup.1 is
a metal selected from chromium (Cr), molybdenum (Mo), and tungsten
(W). Among these, molybdenum and tungsten are preferable, and
tungsten is particularly preferable.
[0058] The neutral ligand represented by L.sup.1 is a ligand that
is neutrally charged when separated from the center metal. Specific
examples of the neutral ligand include, but are not limited to,
ethers such as diethyl ether and tetrahydrofuran; ketones such as
acetone and cyclohexanone; nitriles such as acetonitrile and
benzonitrile; amines such as triethylamine and N,N-diethylaniline;
pyridines such as pyridine and lutidine; phosphines such as
triphenylphosphine; amides such as dimethylformamide; sulfoxides
such as dimethyl sulfoxide; cyclooctadiene; water; carbon monoxide;
arenes such as toluene and xylene; phosphine oxides such as
triphenylphosphine oxide; carbonic acid esters such as ethylene
carbonate; esters such as ethyl acetate; and the like.
[0059] Among these, ethers, pyridines and nitriles are preferable
from the viewpoint of forming a stable transition metal imide
compound.
[0060] The anionic ligand represented by X.sup.1 is a ligand that
is negatively charged when separated from the center metal.
Specific examples of the anionic ligand include, but are not
limited to, a halogen atom such as F, Br, Cl, and I; a hydrido
ligand; a diketonate group such as acetylacetonate; a substituted
or unsubstituted cyclopentadienyl group; a substituted or
unsubstituted allyl group; an alkenyl group; an alkyl group; a
substituted or unsubstituted aryl group; an alkoxy group; a
substituted or unsubstituted aryloxy group; an alkoxycarbonyl
group; a carboxy group; an alkyl sulfonate group; a substituted or
unsubstituted aryl sulfonate group; an alkylthio group; an
alkenylthio group; a substituted or unsubstituted arylthio group;
an alkylsulfonyl group; an alkylsulfinyl group; and the like.
[0061] Among these, a halogen atom, an alkyl group, an aryl group,
an alkoxy group, and an aryloxy group are preferable from the
viewpoint of forming a stable transition metal imide compound.
[0062] Examples of the alkyl group when R.sup.5 represents the
substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, include a linear alkyl group such as a methyl group, an
ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl
group; a branched alkyl group such as an isopropyl group, an
isobutyl group, and a t-butyl group; a cycloalkyl group such as a
cyclohexyl group and an adamantyl group; and the like.
[0063] Examples of a substituent that may substitute the alkyl
group include a halogen atom such as a fluorine atom, a chlorine
atom, and a bromine atom; an aryl group such as a phenyl group; and
the like.
[0064] Examples of the aryl group when R.sup.5 represents the
substituted or unsubstituted aryl group, include a phenyl group, a
1-naphthyl group, a 2-naphthyl group, a 2-biphenyl group, a
4-biphenyl group, and the like.
[0065] Examples of a substituent that may substitute the aryl group
include an alkyl group such as a methyl group, an ethyl group, and
an isopropyl group; a halogen atom such as a fluorine atom, a
chlorine atom, and a bromine atom; and the like.
[0066] Examples of the compound represented by the formula (6)
include tungsten(ethylimido)(tetrachloride)(diethyl ether),
tungsten(ethylimido)(t-butoxide)(trichloride),
tungsten(ethylimido)[di(t-butoxide)](dichloride),
tungsten(ethylimido) [tri(t-butoxide)](ichloride),
tungsten(ethylimido)[tetra(t-butoxide)],
tungsten(ethylimido)(phenoxide)(tetrachloride)(diethyl ether),
tungsten(n-butylimido)(tetrachloride)(tetrahydrofuran),
tungsten(n-hexylimido)(tetrachloride)(diethyl ether),
tungsten(i-propylimido)(tetrachloride)(diethyl ether),
tungsten(cyclohexylimido)(tetrachloride)(diethyl ether),
tungsten(adamantylimido)(tetrachloride)(diethyl ether),
tungsten(benzylimido)(tetrachloride)(diethyl ether),
tungsten(phenylimido)(tetrachloride)(diethyl ether),
tungsten(phenylimido)(tetrachloride)(tetrahydrofuran),
tungsten(2,6-dimethylphenylimido)(tetrachloride)(diethyl ether),
tungsten[2,6-di(i-propyl)(phenylimido)](tetrachloride)(diethyl
ether), and the like. Among these,
tungsten(phenylimido)(tetrachloride)(tetrahydrofuran) is
particularly preferable.
[0067] The compound represented by the formula (6) may be
synthesized using a known method, such as the method disclosed in
JP-A-5-345817, for example. For example, a tungsten imido compound
may be synthesized by reacting tungsten oxytetrachloride with an
isocyanate that includes the desired substituent.
[0068] The compound represented by the formula (6) may be isolated,
purified, and used as the polymerization catalyst, or the reaction
mixture that includes the compound represented by the formula (6)
may be used as the polymerization catalyst in the form of a liquid
without isolating and purifying the compound represented by the
formula (6).
[0069] The transition metal imide compound is normally used so that
the molar ratio ((center metal included in transition metal imide
compound):(norbornene-based monomer)) of the center metal included
in the transition metal imide compound to the norbornene-based
monomer is 1:100 to 1:2,000,000, preferably 1:200 to 1:1,000,000,
and more preferably 1:500 to 1:500,000. If the transition metal
imide compound is used in too large an amount, it may be difficult
to remove the catalyst. If the transition metal imide compound is
used in too small an amount, sufficient polymerization activity may
not be obtained.
[0070] The transition metal imide compound may be used in
combination with an organometallic reducing agent. It is possible
to improve catalytic activity by utilizing the transition metal
imide compound in combination with an organometallic reducing
agent.
[0071] Examples of the organometallic reducing agent include a
compound that includes a hydrocarbon group having 1 to 20 carbon
atoms, and an element among the elements that respectively belong
to Groups 1, 2, 12, 13, and 14 in the periodic table. An
organolithium, an organomagnesium, an organozinc, an
organoaluminum, and an organotin are preferable, and an
organolithium, an organoaluminum, and an organotin are particularly
preferable.
[0072] Examples of the organolithium include methyllithium,
n-butyllithium, neopentyllithium, neophyllithium, phenyllithium,
and the like.
[0073] Examples of the organomagnesium include butylethylmagnesium,
butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride,
n-butylmagnesium chloride, allylmagnesium bromide,
neopentylmagnesium chloride, neophylmagnesium chloride, and the
like.
[0074] Examples of the organozinc include dimethylzinc,
diethylzinc, diphenylzinc, and the like.
[0075] Examples of the organoaluminum include an alkylaluminum such
as trimethylaluminum, triethylaluminum, and triisobutylaluminum; an
alkylaluminum alkoxide such as dimethylaluminum methoxide,
methylaluminum dimethoxide, dimethylaluminum butoxide,
diethylaluminum ethoxide, ethylaluminum diethoxide, and
diisobutylaluminum isobutoxide; an alkylaluminum aryloxide such as
dimethylaluminum phenoxide, diethylaluminum phenoxide, and
diisobutylaluminum phenoxide; an alkylaluminum halide such as
diethylaluminum chloride, ethylaluminum sesquichloride, and
ethylaluminum dichloride; an aluminoxane such as methylaluminoxane,
ethylaluminoxane, and isobutylaluminoxane; and the like.
[0076] Examples of the organotin include tetramethyltin,
tetra(n-butyl)tin, tetraphenyltin, and the like.
[0077] The organometallic reducing agent is used in an appropriate
amount taking account of the type of organometallic reducing agent.
The organometallic reducing agent is preferably used in an amount
of 0.1 to 1,000-fold mol, more preferably 0.2 to 500-fold mol, and
particularly preferably 0.5 to 200-fold mol, based on the center
metal included in the transition metal imide compound. If the
organometallic reducing agent is used in an amount of less than
0.1-fold mol based on the center metal included in the transition
metal imide compound, it may be difficult to sufficiently improve
the polymerization activity. If the organometallic reducing agent
is used in an amount of more than 1,000-fold mol based on the
center metal included in the transition metal imide compound, side
reactions tend to occur.
[0078] When effecting the ring-opening polymerization reaction, a
Lewis base may be added to the polymerization reaction system in
order to control the polymerization rate and the molecular weight
distribution of the resulting ring-opening polymer.
[0079] The Lewis base is not particularly limited. Examples of the
Lewis base include ethers such as diethyl ether and
tetrahydrofuran; ketones such as acetone and cyclohexanone;
nitriles such as acetonitrile and benzonitrile; amines such as
triethylamine and N,N-diethylaniline; pyridines such as pyridine
and lutidine; phosphines such as triphenylphosphine; amides such as
dimethylformamide; sulfoxides such as dimethyl sulfoxide; phosphine
oxides such as triphenylphosphine oxide; esters such as ethyl
acetate; and the like. Among these, ethers, pyridines and nitriles
are preferable.
[0080] The Lewis base is preferably used in an amount of 0.1 to
1,000-fold mol, and more preferably 0.2 to 500-fold mol, based on
the center metal included in the transition metal imide
compound.
[0081] The ring-opening polymerization reaction is normally
effected in an organic solvent. The organic solvent is not
particularly limited as long as the organic solvent does not affect
the polymerization reaction, and dissolves or disperses the
resulting polymer under specific conditions.
[0082] Examples of the organic solvent include an aliphatic
hydrocarbon such as pentane, hexane, and heptane; an alicyclic
hydrocarbon such as cyclopentane, cyclohexane, methylcyclohexane,
dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane,
diethylcyclohexane, decahydronaphthalene, bicycloheptane,
tricyclodecane, hexahydroindenecyclohexane and cyclooctane; an
aromatic hydrocarbon such as benzene, toluene, and xylene; a
halogen-containing aliphatic hydrocarbon such as dichloromethane,
chloroform, and 1,2-dichloroethane; a halogen-containing aromatic
hydrocarbon such as chlorobenzene and dichlorobenzene; a
nitrogen-containing hydrocarbon-based solvent such as nitromethane,
nitrobenzene, and acetonitrile; an ether-based solvent such as
diethyl ether and tetrahydrofuran; an aromatic ether-based solvent
such as anisole and phenetole; and the like.
[0083] Among these, an aromatic hydrocarbon-based solvent, an
aliphatic hydrocarbon-based solvent, an alicyclic hydrocarbon-based
solvent, an ether-based solvent, and an aromatic ether-based
solvent that are widely used industrially are preferable.
[0084] When effecting the ring-opening polymerization reaction, a
molecular weight modifier such as a vinyl compound or a diene
compound may be added to the polymerization reaction system in
order to adjust the molecular weight of the resulting ring-opening
polymer.
[0085] The vinyl compound that may be used to adjust the molecular
weight of the ring-opening polymer is not particularly limited as
long as the vinyl compound is an organic compound that includes a
vinyl group. Examples of the vinyl compound include .alpha.-olefins
such as 1-butene, 1-pentene, 1-hexene, and 1-octene; styrenes such
as styrene and vinyltoluene; ethers such as ethyl vinyl ether,
isobutyl vinyl ether, and allyl glycidyl ether; a
halogen-containing vinyl compound such as allyl chloride; an
oxygen-containing vinyl compound such as allyl acetate, allyl
alcohol, and glycidyl methacrylate; a nitrogen-containing vinyl
compound such as acrylamide; and the like.
[0086] Examples of the diene compound that may be used to adjust
the molecular weight of the ring-opening polymer include a
non-conjugated diene such as 1,4-pentadiene, 1,4-hexadiene,
1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and
2,5-dimethyl-1,5-hexadiene; a conjugated diene such as
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, and 1,3-hexadiene; and the like.
[0087] The molecular weight modifier may be used in an arbitrary
amount within a range from 0.1 mol % to 10 mol % based on the
norbornene-based monomer, for example.
[0088] The concentration of the norbornene-based monomer when
effecting the ring-opening polymerization reaction is not
particularly limited, but is normally 1 to 50 wt %, preferably 2 to
45 wt %, and more preferably 3 to 40 wt %.
[0089] The polymerization temperature is not particularly limited,
but is normally -30 to +200.degree. C., and preferably 0 to
180.degree. C.
[0090] The polymerization time is normally 1 minute to 100
hours.
[0091] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention can be obtained by hydrogenating
the carbon-carbon double bonds included in the cycloolefin
ring-opening polymer obtained by effecting the ring-opening
polymerization reaction as described above in the presence of a
hydrogenation catalyst.
[0092] The hydrogenation catalyst may be a homogeneous catalyst, or
may be a heterogeneous catalyst.
[0093] A homogeneous catalyst has an advantage in that it is easily
dispersed in a hydrogenation reaction mixture, and the amount of
catalyst to be added can be reduced. Since a homogeneous catalyst
exhibits sufficient activity even when the temperature and the
pressure are not increased to a large extent, decomposition and
gelation of the cycloolefin ring-opening polymer and a hydrogenated
product thereof do not easily occur. Therefore, it is preferable to
use a homogeneous catalyst from the viewpoint of cost and the
quality of the product.
[0094] On the other hand, a heterogeneous catalyst has an advantage
in that it exhibits particularly excellent activity at a high
temperature under high pressure, and the cycloolefin ring-opening
polymer can be hydrogenated within a short time.
[0095] Examples of the homogeneous catalyst include a Wilkinson's
complex (chlorotris(triphenylphosphine)rhodium(I)); a catalyst that
includes a combination of a transition metal compound and an
alkylmetal compound (e.g., cobalt acetate and triethylaluminum,
nickel acetylacetonate and triisobutylaluminum, titanocene
dichloride and n-butyllithium, zirconocene dichloride and
sec-butyllithium, and tetrabutoxytitanate and dimethylmagnesium);
and the like.
[0096] Examples of the heterogeneous catalyst include a catalyst in
which a metal (e.g., Ni, Pd, Pt, Ru, and Rh) is supported on a
support. When it is desired to reduce the amount of impurities
included in the resulting hydrogenated product, it is preferable to
use an adsorbent (e.g., alumina and diatomaceous earth) as the
support.
[0097] The hydrogenation reaction is normally effected in an
organic solvent. The organic solvent is not particularly limited as
long as the organic solvent is inert to the hydrogenation reaction.
A hydrocarbon-based solvent is normally used as the organic solvent
since the resulting hydrogenated product can be easily dissolved.
Examples of the hydrocarbon-based solvent include an aromatic
hydrocarbon-based solvent such as benzene, toluene, and xylene; an
aliphatic hydrocarbon-based solvent such as n-pentane, n-hexane,
and n-heptane; an alicyclic hydrocarbon-based solvent such as
cyclohexane, methylcyclohexane, decalin, and bicyclononane; and the
like.
[0098] These organic solvents may be used either alone or in
combination. Since a solvent that is suitable for a ring-opening
polymerization reaction is normally also suitable as a solvent for
a hydrogenation reaction, the hydrogenation catalyst may be added
to the ring-opening polymerization reaction mixture, and the
resulting mixture may be subjected to the hydrogenation
reaction.
[0099] The hydrogenation reaction conditions may be appropriately
selected taking account of the type of hydrogenation catalyst. The
reaction temperature is normally -20 to +250.degree. C., preferably
-10 to +220.degree. C., and more preferably 0 to 200.degree. C.
[0100] The hydrogen pressure is normally 0.01 to 10.0 MPa,
preferably 0.05 to 8.0 MPa, and more preferably 0.1 to 5.0 MPa.
[0101] The hydrogenation reaction time is appropriately selected to
control the hydrogenation rate, but is normally 0.1 to 50
hours.
[0102] After completion of the hydrogenation reaction, the reaction
mixture may be subjected to centrifugation, filtration, and the
like to remove a catalyst residue. If necessary, a catalyst
deactivation agent (e.g., water and alcohol) may be used, or an
adsorbent (e.g., activated clay and alumina) may be added.
Properties of Hydrogenated Cycloolefin Ring-Opening Polymer
[0103] The weight average molecular weight of the hydrogenated
cycloolefin ring-opening polymer according to one embodiment of the
invention is 10,000 to 40,000, preferably 13,000 to 35,000, and
more preferably 15,000 to 30,000. If the weight average molecular
weight of the hydrogenated cycloolefin ring-opening polymer is too
low, the resulting resin formed article may exhibit low mechanical
strength. If the weight average molecular weight of the
hydrogenated cycloolefin ring-opening polymer is too high, the
hydrogenated cycloolefin ring-opening polymer may exhibit
insufficient fluidity when melted, and may exhibit poor
formability.
[0104] The molecular weight distribution (Mw/Mn) of the
hydrogenated cycloolefin ring-opening polymer is not particularly
limited, but is preferably 1 to 5, and more preferably 1 to 4.
[0105] The weight average molecular weight (Mw) and the number
average molecular weight (Mn) of the hydrogenated cycloolefin
ring-opening polymer refer to a standard isoprene-equivalent weight
average molecular weight and a standard isoprene-equivalent number
average molecular weight determined by gel permeation
chromatography (GPC) (eluent: cyclohexane).
[0106] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention has a relatively high glass
transition temperature, and exhibits excellent fluidity upon
melting and excellent mechanical strength.
[0107] The resin formed article (hereinafter may be referred to as
"resin formed article (.alpha.)") obtained by forming the
hydrogenated cycloolefin ring-opening polymer according to one
embodiment of the invention has a glass transition temperature of
140 to 165.degree. C., preferably 145 to 165.degree. C., and more
preferably 145 to 160.degree. C.
[0108] A cycloolefin polymer that produces a resin formed article
(.alpha.) having a glass transition temperature of 140.degree. C.
or more exhibits excellent high-temperature dimensional stability.
A cycloolefin polymer that produces a resin formed article
(.alpha.) having a glass transition temperature of 160.degree. C.
or less exhibits excellent formability.
[0109] The glass transition temperature of the resin formed article
(.alpha.) can be adjusted by appropriately selecting or adjusting
the type and the amount of norbornene-based monomer used to produce
the hydrogenated cycloolefin ring-opening polymer. For example, the
resin formed article (.alpha.) obtained by forming the hydrogenated
cycloolefin ring-opening polymer that includes a large amount of a
repeating unit derived from a tetracyclic norbornene-based monomer
(e.g., tetracyclododecene, 6-ethylidene-2-tetracyclododecene, and
methanotetrahydrofluorene) tends to have a high glass transition
temperature.
[0110] The resin formed article (.alpha.) has a melt flow rate of 8
g/10 min or more, preferably 10 g/10 min or more, and more
preferably 15 g/10 min or more, as measured in accordance with JIS
K 6719 at a temperature of 280.degree. C. under a load of 21.18 N
(2.16 kgf). The upper limit of the melt flow rate is not
particularly limited, but is normally 80 g/10 min or less.
[0111] A hydrogenated cycloolefin ring-opening polymer that
produces a resin formed article (.alpha.) having a melt flow rate
of 8 g/10 min exhibits excellent formability.
[0112] The melt flow rate of the resin formed article (.alpha.) can
be adjusted by appropriately selecting or adjusting the type and
the amount of norbornene-based monomer used to produce the
hydrogenated cycloolefin ring-opening polymer. For example, the
resin formed article (.alpha.) obtained by forming the hydrogenated
cycloolefin ring-opening polymer that includes a large amount of a
repeating unit derived from methanotetrahydrofluorene as a
repeating unit derived from a norbornene-based monomer other than
tetracyclododecene, tends to have a high melt flow rate.
[0113] The melt flow rate of a synthetic resin can be increased by
decreasing the weight average molecular weight of the synthetic
resin. This property can be used in connection with the invention.
However, since the mechanical strength of the resulting resin
formed article may decrease if the weight average molecular weight
is decreased to a large extent, it is preferable to increase the
melt flow rate by appropriately selecting or adjusting the type and
the amount of norbornene-based monomer other than
tetracyclododecene without unduly decreasing the weight average
molecular weight.
[0114] The resin formed article (.alpha.) has a flexural strength
of 60 MPa or more, preferably 62 MPa or more, and more preferably
65 MPa or more, as measured by a flexural test in accordance with
JIS K 7171 at a test speed of 2 mm/min. Note that the details of
the flexural test are described later in connection with the
examples. The upper limit of the flexural strength is not
particularly limited, but is normally 150 MPa or less.
[0115] A hydrogenated cycloolefin ring-opening polymer that
produces a resin formed article (.alpha.) having a flexural
strength of 60 MPa or more exhibits excellent high-temperature
dimensional stability.
[0116] The flexural strength of the resin formed article (.alpha.)
can be adjusted by appropriately selecting or adjusting the type
and the amount of norbornene-based monomer used to produce the
hydrogenated cycloolefin ring-opening polymer. For example, the
resin formed article (.alpha.) obtained by forming the hydrogenated
cycloolefin ring-opening polymer that includes a large amount of a
repeating unit derived from methanotetrahydrofluorene as a
repeating unit derived from a norbornene-based monomer other than
tetracyclododecene, tends to have high flexural strength.
[0117] A resin formed article used as a measurement specimen when
measuring the glass transition temperature, the melt flow rate, and
the flexural strength may include an additive as long as the
measured values are not affected.
[0118] Since the hydrogenated cycloolefin ring-opening polymer
according to one embodiment of the invention meets the requirements
with regard to the structural features and the properties described
above, the hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention exhibits excellent thermal
yellowing resistance, excellent high-temperature dimensional
stability, and excellent formability (i.e., a significant weld line
does not occur).
[0119] The thermal yellowing resistance of the hydrogenated
cycloolefin ring-opening polymer may be evaluated by subjecting the
hydrogenated cycloolefin ring-opening polymer to a test in
accordance with JIS K 7103, and calculating the change in
yellowness index (.DELTA.YI). Note that the details of the test are
described later in connection with the examples.
[0120] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention normally has a change in
yellowness index (.DELTA.YI) of 20 or less, and preferably 15 or
less.
[0121] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention that includes a large amount of
a repeating unit derived from tetracyclododecene, exhibits
excellent thermal yellowing resistance. There is a tendency that
the hydrogenated cycloolefin ring-opening polymer according to one
embodiment of the invention exhibits better thermal yellowing
resistance when the hydrogenated cycloolefin ring-opening polymer
includes a moderate amount of repeating unit derived from
methanotetrahydrofluorene.
[0122] The high-temperature dimensional stability and the
formability of the hydrogenated cycloolefin ring-opening polymer
according to one embodiment of the invention may be evaluated using
the methods described later in connection with the examples.
[0123] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention includes a large amount of a
repeating unit derived from tetracyclododecene. The hydrogenated
cycloolefin ring-opening polymer according to one embodiment of the
invention exhibits improved fluidity upon melting while having a
high glass transition temperature. Therefore, the hydrogenated
cycloolefin ring-opening polymer according to one embodiment of the
invention exhibits excellent high-temperature dimensional
stability.
[0124] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention exhibits improved flexural
strength while having a moderate weight average molecular weight.
Therefore, the hydrogenated cycloolefin ring-opening polymer
according to one embodiment of the invention exhibits excellent
formability.
[0125] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention that has the above
characteristics is useful as a raw material for producing an
optical member for which heat resistance is desired.
2) Resin Formed Article and Optical Member
[0126] A resin formed article according to one embodiment of the
invention is obtained by forming a resin composition that includes
the hydrogenated cycloolefin ring-opening polymer according to one
embodiment of the invention.
[0127] The resin composition may include an additional component
(e.g., additive) as long as the advantageous effects of the
invention are not impaired.
[0128] Examples of the additional component include an antioxidant,
a UV absorber, a light stabilizer, a near-infrared absorber, a
plasticizer, an antistatic agent, and the like.
[0129] Examples of the antioxidant include a phenol-based
antioxidant, a phosphorus-based antioxidant, a sulfur-based
antioxidant, and the like.
[0130] Examples of the phenol-based antioxidant include
3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene,
2,2'-methylenebis(6-t-butyl-4-methylphenol),
4,4'-butylidenebis(3-t-butyl-3-methylphenol),
4,4'-thiobis(6-t-butyl-3-methylphenol), .alpha.-tocopherol,
2,2,4-trimethyl-6-hydroxy-7-t-butylchromane,
tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e, pentaerythritol
tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and the
like. Among these, pentaerythritol
tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] is
particularly preferable.
[0131] When the resin composition includes the phenol-based
antioxidant, the resin composition preferably includes the
phenol-based antioxidant in a ratio of 0.01 to 5 parts by weight,
more preferably 0.1 to 2 parts by weight, and still more preferably
0.2 to 1 part by weight, based on 100 parts by weight of the
hydrogenated cycloolefin ring-opening polymer.
[0132] Examples of the phosphorus-based antioxidant include
distearylpentaerythritol diphosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,
tris(2,4-di-t-butylphenyl) phosphite,
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenyl diphosphite,
trinonylphenyl phosphite, and the like.
[0133] Examples of the sulfur-based antioxidant include distearyl
thiodipropionate, dilauryl thiodipropionate, and the like.
[0134] Examples of the UV absorber include a benzotriazole-based UV
absorber, a benzoate-based UV absorber, a benzophenone-based UV
absorber, an acrylate-based UV absorber, a metal complex-based UV
absorber, and the like.
[0135] Examples of the light stabilizer include a hindered
amine-based light stabilizer.
[0136] Examples of the near-infrared absorber include a
cyanine-based near-infrared absorber, a pyrylium-based infrared
absorber, a squarylium-based near-infrared absorber, a
croconium-based infrared absorber, an azulenium-based near-infrared
absorber, a phthalocyanine-based near-infrared absorber, a dithiol
metal complex-based near-infrared absorber, a naphthoquinone-based
near-infrared absorber, an anthraquinone-based near-infrared
absorber, an indophenol-based near-infrared absorber, an
azide-based near-infrared absorber, and the like.
[0137] Examples of the plasticizer include a phosphoric acid
triester-based plasticizer, a fatty acid monobasic acid ester-based
plasticizer, a dihydric alcohol ester-based plasticizer, an oxy
acid ester-based plasticizer, and the like.
[0138] Examples of the antistatic agent include a fatty acid ester
of a polyhydric alcohol, and the like.
[0139] The content of each additional component may be
appropriately determined taking account of the object. Each
additional component is normally used in a ratio of 0.001 to 5
parts by weight, and preferably 0.01 to 1 part by weight, based on
100 parts by weight of the hydrogenated cycloolefin ring-opening
polymer.
[0140] The resin composition may be prepared by mixing the
components according to an ordinary method. The components may be
mixed in an appropriate solvent, or may be mixed (kneaded) in a
molten state.
[0141] The components may be mixed (kneaded) using a melt mixer
such as a single-screw extruder, a twin-screw extruder, a Banbury
mixer, a kneader, or a feeder ruder. The mixing (kneading)
temperature is preferably 200 to 400.degree. C., and more
preferably 240 to 350.degree. C. The components may be added at a
time, and mixed (kneaded), or may be mixed (kneaded) while adding
the components stepwise.
[0142] The resin formed article according to one embodiment of the
invention may be produced using an arbitrary forming method.
Examples of the forming method include an injection forming method,
a press forming method, an extrusion forming method, and the like.
When the resin formed article is an optical member or the like, it
is preferable to use an injection forming method since the desired
resin formed article can be obtained with high accuracy.
[0143] The melting temperature employed during forming differs
depending on the type of resin composition, but is normally 200 to
400.degree. C., and preferably 210 to 350.degree. C. When a mold is
used, the mold temperature is normally set to 20.degree. C. to
(Tg+15.degree.) C., preferably (Tg-30.degree.) C. to
(Tg+10.degree.) C., and more preferably (Tg-20.degree.) C. to
(Tg+5.degree.) C. Note that Tg is the glass transition temperature
of the resin composition.
[0144] The hydrogenated cycloolefin ring-opening polymer according
to one embodiment of the invention that is used as a raw material
for producing the resin formed article according to one embodiment
of the invention exhibits excellent thermal yellowing resistance,
excellent high-temperature dimensional stability, and excellent
formability, and the resin formed article according to one
embodiment of the invention also exhibits excellent thermal
yellowing resistance, excellent high-temperature dimensional
stability, and excellent formability.
[0145] The resin formed article according to one embodiment of the
invention preferably has a glass transition temperature of 140 to
165.degree. C., a melt flow rate of 8 g/10 min or more as measured
in accordance with JIS K 6719 at a temperature of 280.degree. C.
under a load of 21.18 N (2.16 kgf), and a flexural strength of 60
MPa or more as measured by a flexural test in accordance with JIS K
7171 at a test speed of 2 mm/min.
[0146] The resin formed article according to one embodiment of the
invention is suitably used as an optical member such as an optical
lens, a prism, and a light guide.
[0147] The resin formed article according to one embodiment of the
invention is particularly preferably used as an optical member
(e.g., lens) that is used for a camera installed in an
automobile.
EXAMPLES
[0148] The invention is further described below by way of examples
and comparative examples. Note that the invention is not limited to
the following examples. The units "parts" and "%" used in
connection with the examples respectively refer to "parts by
weight" and "wt %" unless otherwise indicated.
[0149] The properties of the hydrogenated cycloolefin ring-opening
polymer and the like were measured as described below.
(1) Weight Average Molecular Weight
[0150] The weight average molecular weight (Mw) (standard
polyisoprene-equivalent weight average molecular weight) of the
hydrogenated cycloolefin ring-opening polymer was determined by gel
permeation chromatography (GPC) (eluent: cyclohexane).
[0151] Standard polyisoprene (Mw=602, 1390, 3920, 8050, 13,800,
22,700, 58,800, 71,300, 109,000, or 280,000) manufactured by Tosoh
Corporation was used as the standard polyisoprene.
[0152] The molecular weight was measured in a state in which three
columns ("TSKgel G5000HXL", "TSKgel G4000HXL", and "TSKgel
G2000HXL" manufactured by Tosoh Corporation) were connected in
series (flow rate: 1.0 mL/min, sample injection amount: 100 .mu.L,
column temperature: 40.degree. C.).
(2) Glass Transition Temperature (Tg)
[0153] The glass transition temperature of the hydrogenated
cycloolefin ring-opening polymer was measured in accordance with
JIS K 6911 (temperature increase rate: 10.degree. C./min) using a
differential scanning calorimeter ("DSC 6220" manufactured by SII
NanoTechnology Inc.).
(3) Racemo Dyad Ratio
[0154] The racemo diad ratio in the hydrogenated cycloolefin
ring-opening polymer with respect to the repeating unit derived
from tetracyclododecene was determined by subjecting the
hydrogenated cycloolefin ring-opening polymer to .sup.13C-NMR
measurement using deuterated o-dichlorobenzene as a solvent, and
calculating the racemo diad ratio based on the intensity ratio of
the signal (51.7 ppm) attributed to racemo diads to the signal
(51.6 ppm) attributed to meso diads.
(4) Melt Flow Rate (MFR)
[0155] The melt flow rate of the resin composition including the
hydrogenated cycloolefin ring-opening polymer was measured in
accordance with JIS K 6719 at a temperature of 280.degree. C. under
a load of 21.18 N (2.16 kgf).
(5) Flexural Strength
[0156] The pellets of the resin composition including the
hydrogenated cycloolefin ring-opening polymer were introduced into
an injection forming machine ("ROBOSHOT .alpha.-100B" manufactured
by FANUC Corporation), and injection-formed at a resin temperature
of 280.degree. C., a mold temperature of (Tg-15.degree.) C., and an
injection pressure of 100 MPa to prepare a resin sheet having a
length of 80 mm, a width of 10 mm, and a thickness of 4 mm.
[0157] The resin sheet was subjected to a flexural test in
accordance with JIS K 7171 (test speed: 2 mm/min) using an
autograph ("AGS-5kNJ.cndot.TCR2" manufactured by Shimadzu
Corporation) to measure the flexural strength (MPa) of the resin
sheet.
(6) Evaluation of Thermal Yellowing Resistance
[0158] The pellets of the resin composition including the
hydrogenated cycloolefin ring-opening polymer were introduced into
an injection forming machine ("ROBOSHOT .alpha.-100B" manufactured
by FANUC Corporation), and injection-formed at a resin temperature
of 280.degree. C., a mold temperature of (Tg-15.degree.) C., and an
injection pressure of 100 MPa to prepare a resin sheet having a
length of 70 mm, a width of 30 mm, and a thickness of 3 mm.
[0159] The thermal yellowing resistance was evaluated as described
below using the resin sheet as a specimen.
[0160] The specimen was placed in an oven, and heated at
125.degree. C. for 1,000 hours.
[0161] The yellowness index (YI) of the specimen was measured in
accordance with JIS K 7103 using a color difference meter (blank:
air). A value obtained by subtracting the yellowness index (YI) in
air from the measured yellowness index YI was taken as the change
in yellowness index (.DELTA.YI) of the specimen. A small change in
yellowness index (.DELTA.YI) indicates that the specimen yellowed
to only a small extent at a high temperature (i.e., had good
thermal yellowing resistance).
(7) Evaluation of High-Temperature Dimensional Stability
[0162] The pellets of the resin composition including the
hydrogenated cycloolefin ring-opening polymer were introduced into
an injection forming machine ("ROBOSHOT .alpha.-100B" manufactured
by FANUC Corporation), and injection-formed at a resin temperature
of 300.degree. C., a mold temperature of (Tg-5.degree.) C., and an
injection pressure of 40 MPa using a mold (see FIG. 1) designed to
form a lens having a convex surface having a radius of curvature of
5.73 mm, a concave surface having a radius of curvature of 3.01 mm,
a diameter of 4.5 mm (diameter of lens part: 3 mm), and a center
thickness of 0.20 mm, to prepare a resin formed article (lens).
[0163] The dimensions of the resulting lens were measured using an
ultra-precision point autofocus probe 3D measuring instrument
("NH-3 SP" manufactured by Mitaka Kohki Co., Ltd.) within a range
of 1 mm from the center of the lens, and the minimum value of the
dimensional difference from the design value R was subtracted from
maximum value of the dimensional difference from the design value R
to calculate a PV value (micrometers).
[0164] The lens was placed in an oven, and heated at 130.degree. C.
for 170 hours, and the PV value was calculated as described above.
The PV value before heating and the PV value after heating were
compared.
[0165] A small difference between the PV value before heating and
the PV value after heating indicates that the dimensional change at
a high temperature was small.
(8) Evaluation of Formability (by Means of Observation of Weld
Line)
[0166] The surface of the resin formed article (lens) obtained as
described above (see (7)) was observed using a microscope, and the
length of the weld line that occurred in the direction opposite to
the gate was measured. The formability was evaluated in accordance
with the following standard.
Very good: The length of the weld line was less than 1.0 mm. Good:
The length of the weld line was 1.0 mm or more and less than 1.5
mm. Bad: The length of the weld line was 1.5 mm or more.
Example 1
[0167] A polymerization reactor of which the inside had been dried
and in which the internal atmosphere had been replaced by nitrogen,
was charged with 2.0 parts (1% based on the total amount of
monomers subjected to polymerization) of a monomer mixture
including 6-ethylidene-2-tetracyclododecene (ETD) (30%) and
tetracyclododecene (TCD) (70%), 785 parts of dehydrated
cyclohexane, 1.21 parts of a molecular weight modifier (1-hexene),
0.98 parts of a solution (concentration: 19%) prepared by
dissolving diethylaluminum ethoxide in n-hexane, and 11.7 parts of
a solution (concentration: 2.0%) prepared by dissolving
tungsten(phenylimido)tetrachloride-tetrahydrofuran in toluene, and
the mixture was stirred at 50.degree. C. for 10 minutes.
[0168] 198.0 parts of a monomer mixture having the same composition
as described above was continuously added dropwise to the
polymerization reactor over 150 minutes while stirring the mixture
at 50.degree. C. After completion of the dropwise addition, the
mixture was stirred for 30 minutes, and the polymerization reaction
was terminated by adding 4 parts of isopropyl alcohol. The
conversion rate of the monomers into a polymer determined by
subjecting the polymer solution to gas chromatography was 100%.
[0169] 300 parts of the polymer solution was transferred to an
autoclave equipped with a stirrer, and 32 parts of cyclohexane and
3.8 parts of a nickel catalyst supported on diatomaceous earth
("T8400RL" manufactured by Nikki Chemical Co., Ltd., nickel
content: 58%) were added to the polymer solution. After replacing
the internal atmosphere inside the autoclave by hydrogen, the
mixture was reacted at 190.degree. C. for 6 hours under a hydrogen
pressure of 4.5 MPa.
[0170] After completion of the hydrogenation reaction, the mixture
was filtered through a pressure filter ("FUNDABAC filter"
manufactured by IHI Corporation) (filtration bed: diatomaceous
earth ("Radiolite (registered trademark) #500")) under a pressure
of 0.25 MPa to obtain a colorless and transparent solution.
[0171] After the addition of 0.5 parts (based on 100 parts of the
hydrogenated polymer) of pentaerythrityl
tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] ("IRGANOX
(registered trademark) 1010" manufactured by Ciba Specialty
Chemicals Co., Ltd.) (antioxidant) to the solution, foreign matter
was removed by filtration using a filter ("Zeta Plus (registered
trademark) 30H" manufactured by Cuno Filter, pore size: 0.5 to 1
micrometer) and a metal fiber filter (manufactured by Nichidai
Corporation, pore size: 0.4 micrometers).
[0172] The solvent (cyclohexane) and other volatile components were
removed from the filtrate at a temperature of 290.degree. C. under
a pressure of 1 kPa or less using a cylindrical evaporator
(manufactured by Hitachi Ltd.). The residue was extruded in the
shape of a strand in a molten state from a die connected to the
evaporator, cooled with water, and cut using a pelletizer ("OSP-2"
manufactured by Osada Seisakusho) to obtain pellets.
[0173] The above tests and evaluation processes were performed
using the resulting pellets. The results are listed in Table 1.
[0174] Note that the hydrogenation rate achieved by the
hydrogenation reaction was 99% or more (hereinafter the same).
Example 2
[0175] Pellets were obtained in the same manner as in Example 1,
except that a monomer mixture including TCD (80%), ETD (10%), and
dicyclopentadiene (DCPD) (10%) was used, and the tests and the
evaluation processes were performed in the same manner as described
above. The results are listed in Table 1.
Example 3
[0176] Pellets were obtained in the same manner as in Example 1,
except that a monomer mixture including TCD (80%), DCPD (10%), and
methanotetrahydrofluorene (MTF) (10%) was used, and the tests and
the evaluation processes were performed in the same manner as
described above. The results are listed in Table 1.
Example 4
[0177] Pellets were obtained in the same manner as in Example 1,
except that a monomer mixture including TCD (70%), DCPD (10%), and
MTF (20%) was used, and the tests and the evaluation processes were
performed in the same manner as described above. The results are
listed in Table 1.
Comparative Example 1
[0178] Pellets were obtained in the same manner as in Example 1,
except that a monomer mixture including TCD (92%) and norbornene
(NB) (8%) was used, and the amount of 1-hexene (molecular weight
modifier) was changed to 0.8 parts, and the tests and the
evaluation processes were performed in the same manner as described
above. The results are listed in Table 1.
Comparative Example 2
[0179] Pellets were obtained in the same manner as in Example 1,
except that a monomer mixture including TCD (90%) and NB (10%) was
used, and the tests and the evaluation processes were performed in
the same manner as described above. The results are listed in Table
1.
Comparative Example 3
[0180] A polymerization reactor of which the inside had been dried
and in which the internal atmosphere had been replaced by nitrogen,
was charged with 2.0 parts (1% based on the total amount of
monomers subjected to polymerization) of MTF, 785 parts of
dehydrated cyclohexane, 0.86 parts of a molecular weight modifier
(1-hexene), 0.42 parts of diisopropyl ether, 0.11 parts of isobutyl
alcohol, 1.80 parts of a solution (concentration: 15%) prepared by
dissolving triisobutylaluminum in n-hexane, and 13.4 parts of a
solution (concentration: 0.65%) prepared by dissolving tungsten
hexachloride in cyclohexane, and the mixture was stirred at
55.degree. C. for 10 minutes.
[0181] 198.0 parts of MTF and 20.1 parts of a solution
(concentration: 0.65%) prepared by dissolving tungsten hexachloride
in cyclohexane were continuously added dropwise to the
polymerization reactor respectively over 150 minutes while stirring
the mixture at 50.degree. C. After completion of the dropwise
addition, the mixture was stirred for 30 minutes, and the
polymerization reaction was terminated by adding 0.4 parts of
isopropyl alcohol.
[0182] The subsequent steps were performed in the same manner as in
Example 1, and the tests and the evaluation processes were
performed in the same manner as described above. The results are
listed in Table 1.
Comparative Example 4
[0183] Pellets were obtained in the same manner as in Comparative
Example 3, except that the amount of 1-hexene (molecular weight
modifier) was changed to 0.6 parts, 5 parts of a nickel catalyst
supported on alumina ("N163A" manufactured by Nikki Chemical Co.,
Ltd.) was used instead of the nickel catalyst supported on
diatomaceous earth, and the hydrogenation reaction was effected at
a reaction temperature of 230.degree. C. for 8 hours under a
hydrogen pressure of 4.5 MPa, and the tests and the evaluation
processes were performed in the same manner as described above. The
results are listed in Table 1.
Comparative Example 5
[0184] Pellets were obtained in the same manner as in Comparative
Example 3, except that a monomer mixture including TCD (25%), MTF
(70%), and NB (5%) was used instead of MTF, and the amount of
1-hexene (molecular weight modifier) was changed to 1.2 parts, and
the tests and the evaluation processes were performed in the same
manner as described above. The results are listed in Table 1.
TABLE-US-00001 TABLE 1 Example Comparative Example 1 2 3 4 1 2 3 4
5 Monomer TCD 70 80 80 70 92 90 -- -- 25 composition MTF -- -- 10
20 -- -- 100 100 70 (%) NB -- -- -- 8 10 -- -- 5 DCPD -- 10 10 10
-- -- -- -- -- ETD 30 10 -- -- -- -- -- -- -- Racemo diad/meso diad
ratio 85/15 81/19 83/17 78/22 80/20 78/22 -- -- 45/55 Weight
average molecular weight (Mw) 24,000 22,300 23,000 26,000 61,500
29,400 31,500 46,000 19,000 Glass transition temperature (Tg)
(.degree. C.) 151 150 152 151 149 134 156 138 143 Melt flow rate
(g/10 min) 11 21 24 25 2 23 25 24 52 Flexural strength (MPa) 68 79
85 90 79 59 78 111 64 Evaluation of thermal yellowing 11 10 12 15
13 11 45 13 35 resistance (.DELTA.YI) Evaluation of
high-temperature 0.3 0.4 0.2 0.3 0.4 15 0.2 11.6 0.8 dimensional
stability (PV value) Evaluation of formability (by means of Good
Good Good Good Bad Good Good Good Very observation of weld line)
good
[0185] The following were confirmed from the results listed in
Table 1.
[0186] The hydrogenated cycloolefin ring-opening polymers obtained
in Examples 1 to 4 exhibited thermal yellowing resistance,
high-temperature dimensional stability, and formability in a
well-balanced manner.
[0187] The hydrogenated cycloolefin ring-opening polymer obtained
in Comparative Example 1 exhibited excellent mechanical strength,
but had a low melt flow rate, and exhibited inferior formability
since the weight average molecular weight was too high. When the
weight average molecular weight was increased in order to improve
the formability, the resulting hydrogenated cycloolefin
ring-opening polymer exhibited inferior mechanical strength
(Comparative Example 2).
[0188] The hydrogenated cycloolefin ring-opening polymers obtained
in Comparative Examples 2, 4, and 5 had a low glass transition
temperature, and exhibited inferior high-temperature dimensional
stability.
[0189] The hydrogenated cycloolefin ring-opening polymers obtained
in Comparative Examples 3 and 5 that included a large amount of a
repeating unit derived from methanotetrahydrofluorene, exhibited
inferior thermal yellowing resistance. The thermal yellowing
resistance could be improved by changing the hydrogenation reaction
conditions, but the glass transition temperature decreased, and the
high-temperature dimensional stability deteriorated (see
Comparative Example 4).
* * * * *